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CATALYTIC CRACKING OF HYDROCARBONS IN Two STAGES Filed Oct. 18, 1950 l 3 Sheets-Sheet l F UQ .Tl U H Tm: m n r e o v b n b |:O mk@ 5 O mm do... zo....u d.u v mdnmmmd 20|. I um. I...O m M d HH m o.. 9J o 7 All 1k1n 2. n am F E Alm@ L l dokumd dobmzmmd AI vm 0 wm .um 93...". 115.13m .U .b Nm Iv .f IIVV Al OSL ....mik( d4... O* mgl/.dja U dobkzoruddh. 'N mdjmmmd 10.11 ||lh|l|l|| Aww AAI- mail 3 Sheets-Shea*l 2 J. W. PACKIE CATALYTIC CRACKING OF HYDROCARBONS IN TWO STAGES Filed Oct. 18, 1950 J. W. PACKIE CATALYTIC CRACKING OF' HYDROCARBONS IN TWO STAGES 3 Sheets-Sheet 3 Filed Oct. 18, 1950 l:O mk@ AI.

.b5/w. Clbtornef Patented ct. 5, 1954 'i OFFICE CATALYTEC CRACKNG F HYDRCARBNS EN TW@ STAG-ES John W. racine, Maplewood, N. Si., assigner to Standard @il ievelopment Company, a corporation of Delaware i Claims.

The present invention is concerned with an improved process for the rening of petroleum oils. The invention is more specifically concerned with a novel combination of distillation, suspenscid cracking and fluidized solids catalytic cracking processes. In accordance with the present invention, unexpected and desirable results are secured by the handling of the hydrocarbon streams in a manner adapted to secure the desired results utilizing these processing operations.

It is well known in the art to renne petroleum oils by subjecting relatively high boiling fractions of hydrocarbon oils to elevated temperatures and pressures in a manner to produce lower boiling hydrocarbon constituents. IThese refining or cracking operations are carried out either in the presence or in the absence of various catalytic materials. For example, it is well known in the art to conduct a iiuidized solids catalytic cracking operation by subjecting hydrocarbons boiling in the gas oil boiling range and reduced crude boiling range to Contact with solid catalytic particles, which particles are maintained in a state of fluidity by the velocity of upowing gases. It is also known in the art to employ a suspensoid operation and to convert relatively high boiling hydrocarbon constituents to lower boiling constituents by subjecting hydrocarbon feed streams to relatively high temperatures and pressures under conditions wherein catalyst particles are suspended in the liquid feed streams. It has now been found that very desirable results are secured providing these processes are used in combination with one another and in combination with various distillation steps.

For instance if gas oil and reduced Crude are processed in a fluid catalyst reactor as a mixture, the high amount of salt and ash in the reduced crude quickly contaminates the fluidized catalyst adversely affecting its activity `and resulting in poor product yield. Also if highly refractive, or very heavy gas oil boiling in the range of 1000 to 1400" F., is processed in the fluid catalyst reactor, the yield of coke, which must subsequently be burned off the catalyst is undesirably high.

in the present invention these materials are processed in a suspensoid type operation in which they are passed through a nred coil in the presence of a relatively small amount of catalyst (2 to 10 lbs/bbl.) and subjected to high temperatures (SOO-1200" F.) and high pressure (20G-1000 p. s. i. g.) and the catalyst then separated and returned to the iluid catalyst system. The relatively small amount of contaminated catalyst or high carbon catalyst has a greatly reduced effect on the catalyst quality in the fluid catalyst systern. This processing of the reduced crude, or cyclic, or heavy gas oil through a fired coil may be carried out alone or combined with the injection of naphtha for reforming in the same coil.

The present invention may be more fully appreciated by reference to the drawings illustrating embodiments of the same. Figure l illustrates an operation wherein the suspensoid coil outlet is provided with its own cyclone and high pressure product fractionator. Figure 2 illustrates an operation in which a common fractionator is used for the suspensoid and fluidized solids product. Figure 3 illustrates an operation in which the cracked product from the suspensoid furnace is charged directly into the top of the fluidized solids catalyst reactor.

Referring specically to Figure 1, a petroleum heavy or cyclic gas oil or reduced crude fraction is introduced into suspensoid cracking furnace l by means of a feed line 2. If it is also desired'to process a naplitha, it is preferable to introduce the naphtha fraction into the furnace l by means of line 3. Temperature and pressure conditions within the suspensoid furnace l are adapted to secure the desired cracking or conversion of the oil. The cracked products are withdrawn from suspensoid furnace l by means of line l and introduced into cyclones or equivalent means 5 wherein the catalyst particles are separated from the cracked products. The cracked products are removed from the cyclones 5 by means of line 6 and introduced into a high pressure fractionating zone l, with or without quench. A light gas oil fraction is removed by means of line t, while a heavy gas oil fraction is removed by means of line 9. A high boiling tar fraction is removed by means of line l0 while the lower boiling constituents are removed overhead by means of line Il. This gaseous overhead fraction is passed through a condensing zone I2 and introduced into a separator i3 wherein the condensate is separated from the gases, which are removed overhead by means of line lli.- The condensate comprising constituents boiling in the motor fuel boiling range is removed from the bottom of zone I3 by means of line l5 and further handled and processed as desired. A recycle stream is preferably returned to zone 'l by means of line I6.

A hydrocarbon fraction boiling in the gas oil boiling range is introduced into a iiuidized solids catalytic reactor 20 by means of line 2i. This stream is mixed with iiuidized solids catalyst which is introduced into zone 20 by means of line ture and pressure conditions in regeneration zone,Y

24 and catalyst holdup are adjusted to secure the desired burning of the catalyst and to regenerate the same. Regenerated catalyst is removed from zone 24 by means of line 22 and recycled to reaction zone 20. In accordance with the present invention the catalyst segregated in cyclones 5 from the suspensoid operation is preferably introduced by means of line 21 into reaction zone 2Il. However, it is within theconcept of the present invention to introduce` this catalyst into regeneration Zone 24 by means of line 23. Combustion gases are passed through Vsuitable cyclones 28 positioned in the top of regeneration zone 2li and are removed overhead by means of line 29.

Cracked products are removed overhead from reaction zone 2U through cyclones 3! and line 3l, and are introduced into a low pressure fractione ation zone 32. A high boiling gas oil stream is removed from the bottom of zone 32 by means of line 33. Intermediate gas oil boiling streams are removed from zone. 32 by means of lines 34 and 35 respectively. `A fraction comprising hydrocarbon constituents boiling in the motor fuel boiling range is removed overhead from zone 32 by means of line 36, passed through condensing zone 31 and introduced into a separation Zone 38. Uncondensed gases are removed overhead from separation zone 38 by means of line 39 while a hydrocarbonliquid streamv comprising constituents boiling inthe motor fuel boiling range is removed from zone 38 by means of line 4U. It is preferred to recycle a portiony of this liquid product to zone 32 by means of line 4I.

In accordance with the vpresent invention a portion ofthe catalyst regenerated in Zone 24 is segregated by means of line I I mixed with oil to Referring specifically to Figurefz, a cyclic gas, i'

aheavy virgin gas oil, or a reduced crude is introduced in the presence of a catalyst into suspensoid cracking furnace 50 by means of line I. If it is also desired to process a naphtha, this fraction is introduced into zoneV 59 by means of line 52 yas shown.'l Temperature and pressure conditions in Zone 5l) are adapted tosecurethe desired conversion of the relatively high boiling feed fractions to lower boiling constituents; The cracked productsare withdrawn from zone 50 by means of line 53 and introduced into cyclone separators-or equivalent-means 54 wherein solid catalyst particles are'separated from the cracked products. The cracked products are removed from cycloneseparators 54 by means of line 55 and introduced into distillation zone 56,'with or without quench.

A hydrocarbon fraction boiling in the gas oil boiling range isintroducedinto '.fluidized solids catalytic cracking reactor 51 by means of line 58; This feed stream is introduced into line 59 carrying uidized solids lcatalyst from the re generator 6I4 to the reactor 51. Temperature and pressure conditions and catalyst holdup -in theyreactor areadjustedto secure the desired conversion of the oil. Catalyst is withdrawn from the bottom of zone 51 by means of line BI] and passed into regeneration zone 5 I. Temperature and pressure, and catalyst holdup zone GI are adjusted to secure the desired removal of the carbon from the catalyst and to regenerate the same. Airis introduced into the bottom of Zone 6I by means of lines 62 and 53. Regenerated catalyst is withdrawn from zone 5I by means of line 59 and recycled to the reactor 6l. Combustion gases are removed overhead from zone 6I by means of line E4. The cracked products are removed overhead from reactor 51 through cyclones and introduced into Zone 55 by means of line 66.

A heavy tar product is removed from the bottom of zone B6 by means of line 61 while a gas oil fraction is removed by means of line 58. A lower boiling gas oil fraction is removed from zone 55 by means of line 1U and a portion of the same preferably recycled to the top of zone 56f-into an absorber section 51. The gas oil fraction is introduced into the-top of absorber 51 by means of line 58. rlhis stream is preferably cooled to the desired extent by means of heat exchanger 59. Relatively low boiling hydrocarbon'constituentsboiling ybelow the motor fuel boiling range are removed from the absorber section 51 by means of line `5B and handled as desired. A- hydrocarbon fraction comprising constituents boiling in themotor fuel boiling range is removed from zone 55 by means of line 1G,- condensed in condenser 1I and introduced into a separator drum G2. Uncondensed fractions are removed overhead from separation zone 12- and introduced into the bottom of the absorption section 51, by means of line 13.

In accordance with the present invention a portion of the catalyst from regeneration zone 5I' is segregated by means of line |25. This catalyst is mixed with oil to form a slurry in zone I2I and then introduced into the feed to vthe suspensoid operation'by means of line |22.

Referring specifically to Figure 3, a cyclic gasY oil, heavy gas oil, or reduced crude fraction is introduced into la suspenoid cracking zone 35 by means of line` BI. If a gas oil or reduced crude fraction is introducedV into suspenoid cracking zone 80, under certain conditions, it may also be desirable to introduce a hydrocarbon fraction boiling in the motor fuel boiling range into zone SII. If this -type of operation be conducted the naphtha is introduced by means of line 82 as shown. Temperature and pressure conditions are adjusted in zone 20 -to secure the desired conversion of the oil. Ihe cracked product is withdrawn `from zone by means of line 63 and passed with or without quench through reducing valve 84 and then introduced into the upper part of uidized solids reactor 85 above the dense bed. Temperature andgpressure conditions are adjusted in zonef5 to secure the desired conversion of the relatively high boiling constituents to lower boilingconstituents. The cracked products are removed through cyclone separators 86 positioned in thetop of zone 85 andv withdrawn from zone 85 by mea-ns of line 81 and introduced into distillation zone 88. A gas oil fraction is introduced into zone vilbyfnieans of line 89.' This gas oil 'feed stream is introduced into line 98 through Temperature and pressure desired removal of carbon from the catalyst and to regenerate the same. Air is introduced into zone 92 by means of lines 93 and 34. Regenerated catalyst is withdrawn from Zone 92 and recycled to reactor 35 by means of line 00.

A relatively high boiling gas oil, or tar frac tion is removed from the bottom of zone 88 by means of line 95 while a light gas oil fraction is withdrawn by means of line l90 and an intermediate gas oil fraction by means of line S7. A fraction comprising constituents boiling in the motor fuel boiling range is removed from zone 83 by means of line 90, condensed in condenser zone Q0 and passed to a separation zone 00. Constituents boiling in the motor fuel boiling range are removed from separation zone i0@ :by means of line i and handled as desired. Uncondensed gases are removed from lthe tcp of separation zone l by means of line EQ2 and preferably introduced into an absorption zone 02 positioned above zone 88. An absorption oil, preferably segregated from the heavy gas oil fraction, is introduced into the top of absorption zone |02 by means of line H03. Hydrocarbon constituents substantially free of normally liquid constituents are removed from the top of zone 02 by means of line its.

In accordance With the present invention a portion of the catalyst removed from zone 92 is segregated by means of line |05 and mixed with a portion of the feed to the suspensoid operation. IThe slurry or catalyst is introduced into the feed stream by means of line 100.

The present invention is broadly concerned with an integrated distillation operation; a suspensoid operation and a fluidized solids catalytic cracking operation. The invention is more particularly concerned with an operation wherein a hydrocarbon fraction, as for example, one boiling in the heavy gas oil range 100G-1200D F.) or in the reduced crude range (100G-1400" F.) is processed in a suspensoid operation while a gas oil cut (S50-100W F.) is processed in a luidiaed solids catalytic operation. A naphtha fraction (220%450" F.) may also be processed With the foregoing feed stocks. The cracked products are then handled in cyclones and suitable fractionating equipment.

In an operation such as shown in Fig. l, the suspensoid coil outlet is provided With its own cyclone and high pressure product fractionator. The catalyst from the cyclone is transferred to the iiuidized catalyst cracking system by introducing it to the fluidized catalyst reactor or as an alternate to the fiuidiaed catalyst regenerator. Regenerated catalyst is Withdrawn from the fluidized catalyst regenerator and utilized to Iproduce the slurry required in the suspensoid cracking operation.

In an operation illustrated by Fig. 2, a common fractionator is used for the suspensoid and uidized catalytic products. As shown, this fractionator includes an integral absorber. It also may contain a topped crude stripping section in the base of the fractionator.

In an operation disclosed in Fig. 3, the product from the suspensoid furnace is charged directly into the top or the fluidized catalytic reactor utilising the cyclones in this vessel to separate the catalyst from the suspensoid product. At the point of .pressure release on the suspensoid circuit, quenching may be used if desirable.

In accordance With the present invention the process of discharging the whole suspensoid reactor coil outlet stream in the vapor phase directly into the reactor zone of the uidized catalyst unit has a number of advantages. For example it eliminates-the necessity of duplicating cyclone separators. Also the tar Which would condense out on reduction of the temperature from say l0801l10 F. in the suspensoid reactor to 950 in the fluid reactor, may be cracked up in the fluidiaed catalytic reaction Zone. In addition, if no quench is applied the hot products from the suspensoid coil when combined with cracked vapor from the uid bed will be subjected to further cracking. Thus, in effect, an additional processing step is obtained.

The conditions of the suspensoid operation may be varied appreciably depending upon the character of the feed stock beingv processed and depending upon the extent of conversion desired. As pointed out, a suspensoid operation is particularly desirable for the cracking of hydrocarbon fractions boiling in the motor fuel boiling range, (-420 F.) especially in the heavy naphtha boiling range (220-450 F.). It is also desirable for processing residual stocks, as for example, those hydrocarbons boiling in the reduced crude boiling range, 1000 to 1400" F.) as Well as heavy gas oils 10001200 F.). The amount of solid catalyst employed per barrel of oil may vary appreciably, as for example from about 2 lbs. to l0 lbs. of catalyst per barrel of oil. However, it is preferred to use from about 5 to 10 lbs. of catalyst per barrel of oil. rEhe temperatures of the suspensoid operation are in the range from about 800 to 1200 F.

If a reduced crude is being processed, the process is usually in the range from 9l0920 F., Whereas if a naphtha is being processed, the temperatures are of the magnitude of 950-980 F. and higher. Pressures may vary from 200 to 400 lbs. per square inch to as much as 1000 lbs. per square inch.

The iluidized solids technique for processing feed fractions, as for example, petroleum hydrocarbons and for carrying out other chemical reactions, is a conventional one. The system of a uidized solids technique comprises a reaction zone and a regeneration zone, employed in conjunction tvith a fractionation zone. The reactor' and the catalyst regenerator are arranged at approximately an even level. The operation of the reaction zone and the regeneration zone is conventional, which preferably is as follows:

An overflow pan is provided in the regeneration zone at the desired catalyst level. The catalyst overflows into a withdrawal line which preferably has the form of a U-shaped seal leg connecting the regeneration zone with the reaction zone. The feed stream introduced is usually preheated to a temperature in the range from about 500 to 650 F. in exchangers in heat exchange with regenerator ilue gases which are removed overhead from the regeneration Zone, or with cracked products. The heated feed stream is withdrawn from the exchangers and introduced into the reactor. The seal leg is usually sufliciently below the point of feed oil injection to prevent oil vapors from backing into the regenerator in case of normal surges. Since there is no restriction in the overflow line from the regenerator, satisfactory catalyst ovv will occur as long as the catalyst level in the reactor is slightly below the catalyst level in the regenerator when vessels are carried at about the same pressure. Spent catalyst from the reactor flows through a second U-shaped seal leg from the bottom of the reactor into the bottom of the regenerator. The rate of catalyst now is controlled by injecting some of the air into catalyst transfer line to the regenerator.

Thepressure inrthelregenerator may be con'.-` trolled at the desired level by a throttlevalve.

in the overhead line from the regenerator. Thus,

the pressure in the regenerator may be controlled at any desired level by a throttle valve which may be operated, if desired, by a differential pressure controller. If the pressure differential between the two vessels is maintained at a minimum, the seallegs will prevent gases from passing from one vessel into the other in the event that thecatalyst ow in the legs should cease.

Theireactor and the regenerator may be designed for high Velocity operation involving linear superc'ialgasvvelocities. of Afrom about 2.5 to 4 feet .per second. However, the superficialy velocity lof tl'Ieupowing'gases may. vary from about 1-5-:and` higher.: Catalyst losses are minimized and,substantiallyprevented inthe reactor by the use of. multiplestages of .cyclone separators. The.

regeneration: zone isLproVided with cyclone separators. These lcycloneiseparators. are usually from 2 to 3 and morestages.

Distributing. grids may beemployed inthe reaction and.` regeneration` zones. Operating temperatures and pressures'may vary appreciably de.-

pending upon the feed stocks being processed and upon the productsidesired. Operating temperatures' are, for example, in the range from about 800 to 1000?'F., preferably about 850-950 F., in therreaction'zone. Elevated pressures may be employed,abut in general pressures below 100`lbs. per sq. in'. gauge are utilized. Pressures generallyin the range from A1 to30 lbs. per sq. in. gauge are preferred.. A catalyst hold-up corresponding toa space velocity7 of.1 to 20 weights per hour of feed per weight ofcatalyst is utilized. A preferred ratiois 2 to14. Catalyst tooil ratios of about 3 to 10, preferably about 6 to 8 by weight are used.

Thecatalytic material used both in the suspensoid operationand in the vfluidized catalyst crackingfoperation, in accordance with the present invention; are iconventional cracking catalysts. These catalysts-.are'oxides of` metals of Groups II, III, 'IV and V ofA the Periodic Table. A preferred catalystxcomprises :silica-alumina wherein the'weight pericent ofithealumina is inthe range froinabout'5 to` 20%. Another preferred catalystcomprises silica-magnesium where the weight' the catalyst has'a micronsize in the range fromv Under these' conditions with the l about --80 supericial-velocitiesV as given, a iluidized bed is maintainedwherein the lower section of the re- SII actonfa densescatalyst phaseexistspwhile in the;v upperareafofthe reactor a dispersed phasefexists;

Having described theA invention, it Vis claimed: 1. vImproved process Afor Athe conversion of relatively high boiling hydrocarbon constituents into relatively low boiling constituents which comprises, contacting a hydrocarbon feed stream'in a reaction zone in the presence of iiuidized catalytic particles under temperature and pressureconditions adapted to crack said high boiling hydrocarbon constituents, withdrawing catalytic.

maintained under temperature and pressure con-1 ditions adapted to secure the desired conversion of the oil, withdrawing a cracked' product overhead from said reaction zone, withdrawing a cracked product from said suspensoid zone and introducing the samethrough pressure reducing means to the dilute phase zone above said reactionv Zone whereby said cracked products from said suspensoid cracking zone pass through separation means in the top of said reaction Zone and wherein the catalytic particles are separated from said cracked products.

2. Process as dened by claim 1 wherein said catalytic particles comprise silica alumina particles.

3. Process as defined-by claim 1 wherein thepressure in said reaction zone is in the range from about 0-30 lbs. gauge and'wherein the temperature in said reaction zone is in the range from about 800 to'1000o F., and wherein the pressure in said suspensoid zone is inthe range from about 300 to 1000 lbs. and wherein thetemperature in said suspensoid zone is in the range from about 800 to 1100 F.

4. Process as defined by yclaim l wherein thefeed stream introduced into said reaction zone boils in the gas oil boiling range and wherein said second stream introduced into said suspensoid zone boils in the naphtha boiling range.

References Cited in the le of this patent UNITED STATES PATENTS Number Name Date 2,343,649 Egloi Mar. 7, 1944 2,353,731 Kanhofer July 18, 1944 2,382,755 Tyson Aug. 14, 1945 2,488,032 Johnson Nov. 15, 1949 2,521,757 Smith Sept. l2, 1950 2,541,237 Goodson Feb. 13, 1951 

1. IMPROVED PROCESS FOR THE CONVERSION OF RELATIVELY HIGH BOILING HYDROCARBON CONSTITUENTS INTO RELATIVELY LOW BOILING CONSTITUENTS WHICH COMPRISES, CONTACTING A HYDROCARBON FEED STREAM IN A REACTION ZONE IN THE PRESENCE OF FLUIDIZED CATALYTIC PARTICLES UNDER TEMPERATURE AND PRESSURE CONDITIONS ADAPTED TO CRACK SAID HIGH BOILING HYDROCARBON CONSTITUENTS, WITHDRAWING CATALYTIC PARTICLES FROM SAID REACTION ZONE AND REGENERATING THE SAME IN A FLUIDIZED CATALYTIC REGENERATION ZONE, WITHDRAWING REGENERATED PARTICLES FROM SAID REGENERATION ZONE AND RECYCLING A PORTION OF THE SAME TO SAID REACTION ZONE, COMBINING A PORTION OF SAID WITHDRAWN CATALYTIC PARTICLES FROM SAID REGENERATION ZONE WITH A SECOND HYDROCARBON FEED STREAM, PASSING SAID SECOND HYDROCARBON STREAM TO TO A SUSPENSOID CRACKING ZONE MAINTAINED UNDER TEMPERATURE AND PRESSURE CONDITIONS ADAPTED TO SECURE THE DESIRED CONVERSION OF THE OIL, WITHDRAWING A CRACKED PRODUCT OVERHEAD FROM SAID REACTION ZONE, WITHDRAWING A CRACKED PRODUCT FROM SAID SUSPENSOID ZONE AND INTRODUCING THE SAME THROUGH PRESSURE REDUCING MEANS TO THE DILUTE PHASE ZONE ABOVE SAID REACTION ZONE WHEREBY SAID CRACKED PRODUCTS FROM SAID SUSPENSOID CRACKING ZONE PASS THROUGH SEPARATION MEANS IN THE TOP OF SAID REACTION ZONE AND WHEREIN THE CATALYTIC PARTICLES ARE SEPARATED FROM SAID CRACKED PRODUCTS. 